Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
  • C08G59/423—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof containing an atom other than oxygen belonging to a functional groups to C08G59/42, carbon and hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
  • C08G59/56—Amines together with other curing agents
  • C08G59/58—Amines together with other curing agents with polycarboxylic acids or with anhydrides, halides, or low-molecular-weight esters thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
  • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
  • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/6858—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/016—Diazonium salts or compounds
  • G03F7/021—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders
  • G03F7/0212—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders characterised by the polymeric binder or the macromolecular additives other than the diazo resins or the polymeric diazonium compounds

Definitions

• the present invention relates to new polymers and presensitized positive and negative offset printing plates.
• the polymer according to the present invention has a weight average molecular weight value of from 1,200 to 33,000, an amine number (mg HCl/g polymer) of from 1 to 27, and an unsaturation equivalent (milliequivalents of Br 2 /g) of from 400 to 560.
• R' is a covalent bond (ERL-4206 Union Carbide), -COOCH 2 (ERL-4221 Union Carbide), (ERL-4234 Union Carbide), CH 2 -OCO-C 4 H 8 -COO-CH 2 - (ERL-4299 Un. Carb.), or where Z is SO 2 , CH 2 , or
• the compounds of formula (I) have the advantage of producing presensitized positive and negative offset printing plates having both high development speed and high mechanical resistance. Moreover, they are also endowed with high adhesivity to the substrate and this implies the advantage of requiring a lower graining of the support and a lower thickness of the photosensitive layer.
• a second object of this invention is to provide a process for preparing a polymer of the formula I.
• Said process essentially consists of preparing an unsaturated polyhydroxypolyester having an epoxy end group and condensing said epoxy end group with an amino group of a suitable aromatic diamine according to the following scheme: where n,R,Y,X,R',Z',R 2 ,R' 2 ,R 3 ,R' 3 , have the meanings mentioned above in relation to the formula (I).
• Preferred meanigs of (AC) are the following unsaturated aliphatic dicarboxylic acids : maleic, fumaric, muconic, hydromuconic, itaconic, citraconic and mesaconic.
• EP Preferred meanings of (EP) are the followig diepoxides: vinyl cyclohexene dioxide (ERL-4206 Union Carbide), 3,4-epoxycyclohexylmethyl-3,4-epoxy-cyclohexane-carboxylate (ERL-4221 Union Carbide), 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)-cyclohexane-metadioxane (ERL-4234 Union Carbide), bis(3,4-epoxycyclohexyl)-adipate (ERL-4299 Un.Carb.), and diglycidyl ethers of bisphenol A, S, ACP, and F.
• the first reaction step which relates to the preparation of the unsaturated polyhydroxy polyester (II), is preferably carried out by reacting substantially equimolar amounts of (AC) and (EP) in the presence of a suitable accelerating agent at a temperature of from 10 to 150°C, optionally in the presence of one or more suitable inert solvents, until the acidity number of the intermediate product (II) reaches the theoretical value calculated for the desired molecular weight.
• Suitable accelerating agents are AMC1 and AMC2 by Aerojet Strategic Propulsion (chromium salt soluble in organic solvents), p-toluensulphonic acid, triphenylphosphine, and trimethylammonium bromide.
• Suitable organic solvents are butyl acetate, methyl cellosolve, phenyl cellosolve, ethylene glycol dimethyl ether, and ethyl acetate.
• the second reaction step comprises the addition of the aromatic diamine (DM) to the intermediate product (II).
• Said step is preferably performed by adding to the reaction mixture resulting from the first step an amount of (DM) substantially sufficient to react with the epoxy end groups of intermediate (II) at a temperature of from 50 to 150°C.
• the running of the reaction is monitored by means of known analytical techniques (spectrophotometry FTIR and/or primary amine number).
• antioxidant agents such as, for example, hydroquinone, 2,6-di-terbutyl-p.cresole, butyraldoxime, 1,5-naphthalenediol, di-hydroxyazobenzene, 2-mercaptobenzothiazole, and the like.
• a further object of this invention is to provide a presensitized positive or negative offset printing plate formed by a layer sensitive to the light having wavelength of from 200 to 500 nm spread on a suitable support, said photosensitive layer comprising essentially a polymer, a photosensitive diazocompound, a dye and a compound selected from photoinitiators, sensitizers, and diazides, characterized in that the polymer is a compound of the formula (I).
• the support is preferably a metal sheet, e.g. aluminium, suitably treated according to known techniques such as degreasing, pickling, graining, buffing, electrochemical anodization, surface protection treatments and the like.
• known techniques such as degreasing, pickling, graining, buffing, electrochemical anodization, surface protection treatments and the like.
• the diazocompounds present in photosensitive compositions according to the present invention are consisting of positive or negative light-sensitive diazocompounds commonly used for lithographic printing plates.
• these compounds are aromatic diazocompounds wich have been condensed with products containing reactive carbonyl groups such as formaldehyde and paraformaldehyde.
• Said diazocompounds may be reacted with copulating agents such as, e.g., aromatic acid compounds such as benzenesulphonate, toluenesulphonate, unsubstituted or substituted sulphonated benzophenones.
• a dye has substantially the aim of enabling to visualize the non-exposed portions with respect to those exposed to a lamp having an emission spectrum coprised within 200 and 500 nm.
• a dye is preferably used any known dye that is compatible with the other components of the photosensitive layer and is easily removable by the developing bath from the non-exposed portions.
• Dodecyl-, decyl-, nonyl-, and octylbenzenesulphonate, dodecyl-, decyl-, nonyl-, and octylsulphonate of organic and inorganic bases, and the mixture thereof are examples of suitable alkyl- and alkylbenzene-sulphonates.
• suitable organic and inorganic bases are: triethanolamine, sodium, potassium and lithium.
• a specific example of a suitable developing composition comprises: 1,000 g of Sulfetal TL 40TM by Zschimmer & Schwarz, 600 g of phenyl glycol by BASF, 100 of sodium metasilicate pentahydrate by A.C.E.F. (Italy), and 2,300 of deionized water.
• the mixture was stirred at room temperature for 5 minutes and then brought to 80°C. Upon reaching 80°C, 6.68 g of AMC-2 (0.04 moles), catalyst consisting of an organic chromium salt manufactured by Aerojet Strategic Propulsion Co. U.S.A, diluted in 58.1 g of butyl acetate (0.5 moles), were added in about 30 minutes. The temperature was then raised to 100°C and maintained until the acid number of the product was of 20 mg KOH/g. 91.3 g of methylcellosolve (1.2 moles) were then added and the temperature was reduced very qickly to 50°C. The acid number of the thus obtained product was of 18 mg KOH/g and the weight average molecular weight value of 16,000.
• the photosensitive composition of this invention mainly comprises the following ingredients: Parts (w/w) (P) polymer of the formula (I) according to this invention 68.5-74.0 (DZ) diazo compound 20.0-12.0 (CO) dye 2.5- 3.0 (FO) photoinitiator or (SE) sensitizer or (ZD) diazide 6.5-8.0 (LI) levelling agent 2.3- 3.0 dissolved in 1,500-1,700 parts of a diluent mixture or in a non-aqueous and non-reactive diluent.
• non-reactive diluents is intended to mean all those diluents which cannot undergo reaction under the action of light beams having a wavelenght of from 180 to 550 nanometers or heat to form polymers or condensates.
• the thus obtained photosensitive printing plate was dried in an infrared oven, with forced ventilation, for 3 minutes at a temperature of 70°C. After cooling, the plate was stored in a dark place where the humidity degree was 60%, protected from air by means of a sealed polyethylene sheet.
• the final weight of the photosensitive coating composition was of 0.9 g/m 2 .
• the photosensitive printing plates L1-L52 prepared as described in Examples 22-74 above, were exposed, developed and evaluated for a number of properties enabling to assess their performances in conditions of actual use.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• General Physics & Mathematics (AREA)
• Materials For Photolithography (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Polymerisation Methods In General (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
• Laminated Bodies (AREA)
• Printing Methods (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)
• Graft Or Block Polymers (AREA)
• Plural Heterocyclic Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Nitrogen Condensed Heterocyclic Rings (AREA)

Applications Claiming Priority (3)

Publications (2)

Family

ID=11195388

Family Applications (1)

Country Status (7)

Family Cites Families (3)

• 1990
  • 1990-12-13 IT IT02237390A patent/IT1245307B/it active IP Right Grant
• 1991
  • 1991-12-06 AT AT91920857T patent/ATE157379T1/de active
  • 1991-12-06 ES ES91920857T patent/ES2108050T3/es not_active Expired - Lifetime
  • 1991-12-06 EP EP91920857A patent/EP0561847B1/en not_active Expired - Lifetime
  • 1991-12-06 AU AU90204/91A patent/AU9020491A/en not_active Abandoned
  • 1991-12-06 DE DE69127460T patent/DE69127460T2/de not_active Expired - Fee Related
  • 1991-12-06 WO PCT/EP1991/002349 patent/WO1992010523A1/en not_active Ceased

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